EP1057052A1

EP1057052A1 - Method for producing a structure of interference coloured filters

Info

Publication number: EP1057052A1
Application number: EP99900426A
Authority: EP
Inventors: Johannes Edlinger; Reinhard Sperger; Maria Simotti
Original assignee: Unaxis Trading AG
Current assignee: Oerlikon Surface Solutions AG Pfaeffikon
Priority date: 1998-02-20
Filing date: 1999-01-21
Publication date: 2000-12-06
Anticipated expiration: 2019-01-21
Also published as: US7632629B2; JP2002504699A; US6468703B1; WO1999042864A1; EP1057052B2; CH693076A5; EP1437606A3; EP1437606B1; US20050157414A1; EP1057052B8; US6879450B2; ES2214837T3; EP1057052B1; TW420823B; JP2010009078A; US20020196568A1; JP4871987B2; JP5113879B2; EP1437606A2; JP2010250329A

Abstract

The present invention relates to a method for producing a structure for a layered system of coloured filters on a substrate. According to this method, a structured paint layer is applied according to a lift-off technique to produce areas with surfaces comprising a paint layer and areas without any paint layer, after which a layered system of coloured filters is applied. The areas of the layered system of coloured filters, which are applied on the top, are further removed together with the areas comprising surfaces with a paint layer. The layered system of coloured filters (31) is applied according to a plasma-assisted coating method at a temperature not exceeding 150° C.

Description

Process for producing a structure of interference color filters

The present invention relates to a method for producing a color filter layer system structure on a base, in which, using lift-off technology, a structured lacquer layer is deposited, with lacquer layer surface areas and areas without lacquer layer, then a color filter layer system is deposited and finally with the lacquer layer surface - the areas of the color filter layer system deposited thereon are removed.

Such a technique is known as a lift-off technique. It is relatively inexpensive because relatively few process steps have to be carried out in a vacuum atmosphere. This technique is known for example from US-A-3,914,464:

A photoresist or a metal layer with a predetermined thickness of, for example, 4 to 6 μm is deposited as the lift-off mask, and a dielectric interference color filter layer system of only half the thickness is deposited over it. Before the color filter layer system is separated, the lift-off lacquer is cured in a vacuum atmosphere for a long time, over 8 hours at 200 ° C. The lift-off varnish or its structured surfaces are removed after the color filter layer system has been deposited with hot xylene in the actual lift-off step.

It is striking that the lift-off lacquer layer structure is treated in a complex manner, in such a way that vapor deposition can be used as a deposition method for the color filter layer system. To ensure that the quality of the - 2 -

to ensure different system layers, a vapor deposition temperature of over 200 ° C must be maintained. The underlying paint layer must therefore withstand these temperatures without change.

It is further from the literature, e.g. from H.A. MACLEOD, "Thin-Film Optical Filters" 2nd edition, Adam Hilger Ltd., 1986, pages 357 to 405, discloses that evaporated optical layers are not spectrally stable at lower temperatures. Their spectral properties change with the ambient temperature and air humidity, with the cut-on and cut-off edges of the spectral characteristic in particular being spectrally shifted. If you want to deposit spectrally stable layers that are of sufficient quality, the evaporation temperature must be selected to be very high, which leads to the fact that the underlying paint polymerizes and the subsequent lift-off process is extremely difficult. If, on the other hand, an attempt is made to keep the temperature of the vapor deposition process low, one buys this, as mentioned, by strong temperature and humidity-dependent spectral shifts in the edges mentioned.

Furthermore, the long baking out of the lacquer in vacuum, which is proposed in the abovementioned document, is extremely costly and significantly reduces the output rate of production systems for structures of this type. Furthermore, the use of hot xylene to dissolve the varnish, which is comparatively high-temperature resistant, is highly questionable with regard to the carcinogenicity of xylene. Because furthermore, due to the application process of the color filter layer system at temperatures well above 200 ° C, a lacquer layer withstanding these temperatures is provided - 3 -

must be provided for the subsequent removal of the paint large contact surfaces for the solvent. For this reason, the thickness of the lacquer layer must be selected to be significantly higher than the thickness of the color filter layer systems to be deposited. This results in large, disturbed zones: If, after the lacquering and structuring of the lacquer layer, a color filter subsystem is separated into lacquer- and lacquer-free areas, the result is, as shown in FIG. 1, because of the shadowing by the edges the paint areas 1, in the edge areas 3 of the color filter structure, disturbed zones in which the color filter structure thickness is smaller than in undisturbed areas 5. The greater the paint thickness d, the larger the disturbed color filter structure areas.

In addition, it is known that substrate glasses shrink at the temperatures necessary for the vapor deposition of the color filter layer systems mentioned, i.e. change their shape. This means that the side-by-side deposition of color filter layer systems with different spectra, such as for example for red, yellow and blue, cannot be carried out geometrically exactly, which leads to blurring between filter areas of different spectral areas.

Furthermore, the glass substrate becomes brittle at the high temperatures mentioned, in particular taking into account the thermal alternating stress, for example when depositing several color filter layer systems in succession using lift-off technology. This leads to an impairment of the breaking strength of the structures produced and thus to an increase in failure. Another alternative would be to use a paint that can withstand the high evaporation temperatures required, i.e. temperatures in the range of 300 ° C. However, such varnishes are expensive and difficult to process.

You could also use metal liftoff masks, e.g. use from AI or Cr. However, since their application usually requires a vacuum coating step again, this would also be too expensive.

It is an object of the present invention, based on a method of the type mentioned above, to remedy the disadvantages mentioned. This is achieved when the method mentioned is carried out according to the characterizing part of claim 1.

This enables the lift-off lacquer to be subjected to much less thermal stress when the filter layer systems are deposited, ie far below the polymerization temperature of conventional photoresists, for example. The proposed plasma-assisted deposition processes, in which the substrate is exposed to a high ion bombardment density, preferably by means of plasma-assisted vapor deposition or sputtering, also result in filters with dense layers and with spectral properties that are stable in terms of temperature and moisture. Because the paint is thermally less stressed, its necessary thermal resistance can be significantly reduced, which in turn means that a considerably shorter paint treatment and significantly reduced paint layer thicknesses are required, which in turn reduces the extent of the disturbed areas 3 according to FIG. 1. In addition, conventional photoresists can be used and - 5 -

using conventional solvents such as acetone or NMP (N-methyl-2-pyrrolidone) for the lift-off.

The method according to the present invention

• consequently results in significantly reduced coating temperatures, which leads to a reduction in the necessary coating thickness and the usability of conventional, inexpensive coatings. The further reduction in paint thickness leads directly to a reduction in the extent of the interference areas in accordance with FIG. 1.

• The plasma support of the coating, be it through the generation of charged particles in a separate plasma chamber, extraction through grids in the coating room or through plasma generation in the coating room, results in bombardment of the substrates with a high-density ion current, which means dense, optically stable filter layers will be realized.

• The extent of the interferences caused by shadowing can be reduced by additional guideline measures, such as the provision of collimators or by electrostatic alignment of the ion movement. The lowest possible pressures are also used in the coating chamber, with a correspondingly larger mean free path.

If sputtering is used without providing additional directional measures, then, according to FIG. 1, there are disturbed areas 3 with an extent of approximately 5 * d, with more directed plasma-assisted methods down to approximately 1 * d. This in the case of the values for d. - 6 -

A more directional coating process than sputtering is plasma-assisted evaporation, in which, as is known, material from an evaporation crucible is thermally evaporated into the process atmosphere, for example by electron beam evaporation, a plasma being maintained in the atmosphere. This eliminates the problem of shadowing even more, and it is also possible to master color filter layer system structures with very small dimensions and to deposit them with high efficiency.

The proposed method is particularly suitable for color filter structuring for LCD projectors and CCD sensors.

The invention is explained below with reference to figures, for example.

These show:

1: a schematic representation of a coated, structured and coated substrate to explain the formation of disturbed areas,

2 shows schematically a sputter coating installation suitable for carrying out the method according to the invention in schematic form,

3: a system suitable for carrying out the method according to the invention for plasma-assisted thermal evaporation, again shown schematically, 4: schematically, a lacquer structure deposited on a substrate and its rounding of the subsequent coating and

5: in a representation analogous to FIG. 4, the provision of an intermediate layer between the lacquer structure and the subsequently deposited filter layer in order to avoid the rounding of the edges of the photoresist explained with reference to FIG. 4.

2 schematically shows a first embodiment variant of a system for sputtering used according to the invention. A plasma 13 is maintained via a sputter source 10 with material to be sputtered, such as a magnetron source. Ions of a supplied working gas AG, such as Ar, strike predominantly neutral target material particles N from the target due to pulse transmission, which deposit on the workpiece 15. As shown schematically on the feed unit 17, the plasma can be DC or a pulsed DC voltage over the sputter source

PL or basically by means of superimposed DC and AC or with AC, in particular with RF, power. Due to the deposition of dielectric layers of interest on the usually non-conductive workpiece substrates 15, which is of interest in the present case, reference is made in particular to the possibility of operating the plasma by means of a direct voltage, but the plasma-generating electrodes, shown schematically in FIG. 2 at 19a and 19b, and how thereon indicated by dashed lines, in predetermined time intervals, preferably periodically, to connect with low resistance. With regard to the plasma-assisted coating of non-conductive substrates with dielectric layer - 8th -

and using DC plasmas or substrate bias, reference may be made to: EP-508 359 or US Pat. No. 5,423,970; - EP-564 789 or the US applications

US SN 08/300865 US SN 08/641707.

The layers of the color filter layer systems are each either non-reactive, that is to say exclusively using working gas AG and / or by a reactive sputtering process and using a reactive gas RG, as generated by 0 ₂ , for example depending on which layer materials are used. According to the invention, temperatures of the coated workpieces 15 provided with the lift-off lacquer 11 of at most 150 ° C., preferably at most 100 ° C., are maintained.

Due to the high ion bombardment density, dense layers are realized which hardly change their spectral properties with changing ambient temperature and air humidity.

Without further directional measures, such as the provision of collimators, the sputter coating according to the invention is suitable for applications in which disturbed areas 3 according to FIG. 1 with an extension of approximately 5 * d can be accepted.

In FIG. 3, in a manner analogous to FIG. 1, a second method used according to the invention is shown schematically, namely plasma-assisted or ion-assisted evaporation. In this case, material from a crucible 27 is used, for example, by means of an electron beam 23 and / or a heater 25. - 9 -

steams. Again, a dense plasma 24 is maintained above the crucible 27 with a feed source 28, which, as far as the output signals are concerned, can be constructed analogously to the source 17 explained with reference to FIG. 2. The workpieces are preferably attached to a rotatably driven carrier dome 26, the center of which is the center Z of the evaporation source 27. Again temperatures of at most 150 ° C are maintained, especially at most 100 ° C. This directed method makes it possible to coat lift-off lacquer structures 11 with filter layer systems which are disrupted

Areas 3 according to Fig. 1 require, the extent of which is approximately 1 * d and less.

In plasma-assisted or ion-assisted evaporation according to FIG. 3, depending on the layer to be built up, the

Color filter layer system worked non-reactively using only the working gas AG, or reactively using a reactive gas RG.

In FIG. 4, the lift-off on the substrate 30 is enlarged.

Paint structure 32 shown. The plasma 34 of the plasma-assisted deposition process is shown schematically above this. If the first layer 31 of the color filter layer system, shown in broken lines in FIG. 4, is to be deposited by a reactive process, such as in particular using ionized oxygen, then the lift-off lacquer structure, as indicated schematically at 35, is especially in the edge areas attacked by excited reactive gas, as mentioned in particular 0 ₂ or by H ₂ 0 activated and / or split in the plasma from the residual gas. - 10 -

A first possibility to prevent this is to lay down the first layer of the color filter layer system non-reactively, ie with a view to FIG. 2 or FIG. 3 using exclusively the working gas Ar. For this purpose, the layer material is either used directly as the target or evaporation source material.

A second and preferred possibility according to FIG. 5 is to apply an optically broadband and largely losslessly transmitting, ie optically neutral, well-adhering intermediate layer to the lift-off lacquer structure before applying the first layer 31 of the color filter layer system. as a protective layer that withstands the subsequent process. The intermediate layer 45 shown in FIG. 5 with a thickness of 5 to 10 nm preferably consists of SiO or SiO ₂ , which is not chemically attacked by excited ionized reactive gas, in particular 0 ₂ or H ₂ 0 from the residual gas. In FIG. 5, the layer 31 entered with dashed lines denotes the subsequently applied first optically active layer of the color filter layer system, which can now be deposited by a reactive process. Furthermore, the intermediate layer 45 can also consist of SiO ₂ , which is deposited non-reactive or only weakly reactive. An Si0 ₂ intermediate layer then forms the first, lower refractive index layer of the filter layer system with the following, higher refractive index layers.

Coating processes with the resulting color filter structures, for example, are presented below. - 11

Example 1:

- Substrate: glass

- filter structure: strips 160 μm wide,

20 mm long, 100 μm distance

- Lacquer layer thickness: 3.2 μm

- Lacquer: Shipley 1045, diluted 6: 1.

- opt. Filter layer system: 1.5 μm (d ₅ of FIG. 1)

- Layer system: Si0 ₂ / Ti0 ₂

Coating process Si0 ₂ : reactive sputtering, system BAS 767

- Source: Si-Target

- Sputtering power: 6.4 kW

- Working gas: Ar

- Reactive gas: 0 ₂

- Flow working gas 40 sccm

- Reactive gas flow: 50 sccm

- Rate: 0.3 nm / sec

- Coating process Ti0 ₂ : reactive sputtering

- Source: Ti-Target

- Sputtering power: 10 kW

- Working gas: Ar

- Reactive gas: 0 ₂

- Working gas flow: 40 sccm

- Reactive gas flow: 36 sccm

- Rate: 0.16 nm / sec

- Coating temperature: T <80 ° C Results:

Size of the disturbed zone next to the paint mask (1 of Fig. 1): <10 μm

Stability of the edges of the filter: <1 nm edge shift from - 12 -

20 ° C to 80 ° C

In this example, the intermediate layer is omitted. The plasma is switched on before the actual coating begins. Therefore, the paint mask comes into contact with 02 / Ar plasma. This rounds off the edges of the paint. This complicates the lift-off step or makes a relatively thick paint mask necessary.

Example 2:

- Substrate: glass

- Filter structure: strips 10 x 10 μm to 100 x 100 μm

- Lacquer layer thickness (d): 0.5 μm - 2 μm

- opt. Filter layer (d ₅ ): 1.4 μm - varnish: Shipley 1045, dilution 6: 1 to

1: 1

- Layer system: intermediate layer SiO, 10 nm thick,

Si0 ₂ / Ti0 ₂

- Coating process: SiO intermediate layer non-reactive without plasma support, Si0 ₂ / Ti0 ₂ system plasma-supported

Evaporation, system LEYBOLD APS 1100

SiO non-reactive, without APS plasma source:

- Source e-beam evaporator with four-hole crucible, SiO granules - rate: 0.1 nm / sec

- System: BAS 767

- Pressure: 1 * 10 ^"5 mbar

Si0 ₂ : reactive vapor deposition with APS plasma source 13

- Source: E-jet evaporator with four-hole crucible, Si0 ₂ granulate

- Rate: 0.6 m / sec

APS plasma source:

- Discharge current: 50 A.

- Bias voltage: 150 V

- U anode cathode: 130 V

- Working gas: Ar

- Reactive gas: 0 ₂

- Working gas flow: 15 sccm

- Reactive gas flow: 10 sccm

- Total pressure: 3.5 * 10 ^"3 mbar

Ti0 ₂ : reactive vapor deposition with APS plasma source - source: e-jet evaporator with four-hole crucible, TiO tablets

- Rate: 0.3 m / sec

APS plasma source:

- Discharge current: 50 A - bias voltage: 110 - 120 V

- U anode cathode: 100 - 110 V

- Working gas: Ar

- Reactive gas: 0 ₂

- flow of working gas; 11 sccm - Reactive gas flow: 35 sccm

- Total pressure: 4.2 * 10 ^"3 mbar

Coating temperature: T <105 ° C

Results: Stability: <1 nm spectral edge shift from 20 ° C to 80 ° C - 14 -

Size (1) of the disturbed zone: <2 μm

The procedure according to the invention makes it possible to produce pixel structures, such as in particular for LCD light valve projectors and CCD sensors, inexpensively and with a low reject rate, which are also spectrally extremely stable with respect to environmental changes, in particular changes in temperature and humidity . Particularly when using the intermediate layer mentioned above, extremely good adhesion of the color filter systems to the substrate is also achieved.

The necessary lift-off lacquer layers can be much thinner than double the color filter layer systems placed on top. The provision of overhanging side walls of the lacquer areas, as is customary in the case of aluminization in semiconductor production, is superfluous.

Because the color filter layer systems are applied at low temperatures and the underlying lift-off lacquer structures are exposed to correspondingly low temperature loads - and therefore only have to be slightly temperature-resistant - the result is a highly simplified lift-off technique without the need for hot and highly aggressive ones Solvents or ultrasound would have to be used for the lift-off.

The preferred use of the intermediate layer mentioned avoids the negative influence on the reactive deposition of the first filter layer on the lift-off lacquer, in particular the damage to the edges of the lacquer structures by reactive Ar-0 ₂ -H ₂ 0 plasmas.

Claims

- 15 patent claims:

1. Process for producing a color filter layer system structure on a base, in which, using lift-off technology, a structured lacquer layer is deposited on the base, with lacquer layer surface areas and areas free of lacquer layer, then a color filter layer system is deposited and then with the areas of the color filter layer system deposited thereon are removed from the lacquer layer surface areas, characterized in that the color filter layer system is deposited by a plasma-assisted coating at a temperature of at most 150 ° C.

2. The method according to claim 1, characterized in that the depositing is carried out by sputtering or plasma-assisted vapor deposition.

3. The method according to claim 1, characterized in that the depositing is supported by a low-voltage arc discharge.

4. The method according to any one of claims 1 to 3, characterized in that the depositing of the color filter layer system takes place at a temperature of at most 100 ° C.

5. The method according to any one of claims 1 to 4, characterized in that the plasma is generated by means of DC or AC, in particular RF or a pulsating DC voltage or by means of superimposed AC and DC. - 16 -

6. The method according to any one of claims 1 to 4, characterized in that the depositing of at least one layer of the color filter layer system is carried out in a reactive gas atmosphere.

7. The method according to any one of claims 1 to 5, characterized in that the first layer of the color filter layer system is deposited in an atmosphere containing noble gas or oxygen.

8. The method according to any one of claims 1 to 6, characterized in that the color filter layer system comprises layers with a higher and layers with a lower refractive index.

9. The method according to any one of claims 1 to 8, characterized in that an optically essentially neutral intermediate layer is applied as the first layer on the lacquer layer, which intermediate layer is more stable with respect to the subsequently used coating atmosphere than the lacquer layer, which is preferably 5 nm to 10 nm thick and more preferably consists of SiO or Si0 ₂ .

10. The method according to any one of claims 1 to 7, characterized in that the layers are deposited with the preferred direction of impact of the layer material perpendicular to the base.

11. Color filter surface structure, deposited on a substrate as a field of color filter layer systems, characterized in that the first layer of the color filter layer systems facing the substrate is an optically essentially neutral layer, which preferably consists of SiO ₂ or SiO. - 17 -

12. Use of the method according to one of claims 1 to 10 or the structure according to claim 11 for the production of color filters for LCD Lightvalve projectors or for the coloring for CCD sensors.